Flexible curable heterochain polymers

ABSTRACT

POLYMERIC MATERIALS USEFUL FOR FURTHER REACTION WITH PHENOL FORMALDEHYDE RESINS TO MAKE COMPOSITIONS USEFUL FOR INTERIOR CAN COATINGS, DRUM AND PAIL LININGS, WIRE COATINGS, LAMINATING RESINS, BAKING PRIMERS, ADHESIVES, PIPE COATINGS, PHENOLIC MOLDING RESINS, FORUDRY RESINS AND THE LIKE ARE PRODUCED BY THE METHOD COMPRISING STEPS OF: (1) REACTING A POLYMER CONTAINING ALPHA, BETA-CARBONTO-CABON UNSATURATED CARBONYL FUNCTION WITH A NUCLEOPHILIC COMPOUND HAVING AT LEAST TWO ACTIVE HYDROGENS TO FORM A POLYMER CONTAINING AN ACTIVE PENDANT NUCLEOPHILIC GROUP CONTAINING AT LEAST ONE ACTIVE HYDROGEN. (2) REACTING THE RESULTANT NUCLEOPHILIC GROUP CONTAINING ACTIVE HYDROGEN ON THE SAID POLYMER WITH AN ALDHYDE TO FORM A POLYMER CONTAINING AN ACTIVE PENDANT METHYLOL DERIVATIVE GROUP. THE ABOVE STEPS MAY BE CARRIED OUT AS A SEPARATE REACTION AND SEPARATELY CONTROLLED TO GIVE THE RESULTANT DESIRED POLYMER PROPERTIES IN A SINGLE REACTION VESSEL IN SEQUENCE.

United States Patent 3,647,757 Patented Mar. 7, 1972 3,647,757 FLEXIBLE, CURABLE HETEROCHAIN POLYMERS Sung Ki Lee, Niagara Falls, N.Y., assiguor to Hooker Chemical Corporation, Niagara Falls, N.Y.

No Drawing. Continuation-impart of application Ser. No. 569,943, Aug. 1, 1966, now Patent No. 3,489,701. This application Dec. 29, 1969, Ser. No. 888,839

Int. Cl. C08g 17/14, 13/00 US. Cl. 260-725 11 Claims ABSTRACT OF THE DISCLOSURE Polymeric materials useful for further reaction with phenol formaldehyde resins to make compositions useful for interior can coatings, drum and pail linings, wire coatings, laminating resins, baking primers, adhesives, pipe coatings, phenolic molding resins, foundry resins and the like are produced by the method comprising steps of:

(l) Reacting a polymer containing alpha,beta-carbonto-carbon unsaturated carbonyl function with a nucleophilic compound having at least two active hydrogens to form a polymer containing an active pendant nucleophilic group containing at least one active hydrogen.

(2) Reacting the resultant nucleophilic group containing active hydrogen on the said polymer with an aldehyde to form a polymer containing an active pendant methylol derivative group.

The above steps may be carried out as a separate reaction and separately controlled to give the resultant desired polymer properties in a single reaction vessel in sequence.

REFERENCE TO 'PRIOR APPLICATION This is a continuation-in-part of Ser. No. 569,043 filed Aug. 1, 1966, now U.S. Pat. 3,489,701.

This invention relates to flexible phenolic resins. More particularly, this invention relates to a method for preparing a flexible phenolic polymer which has good flexibility, impact resistance and color stability, by condensing a heterochain polymer containing an u,B-car-bon-to-carbon unsaturated carbonyl group with a phenolic compound.

I-Ieretofore, the relatively poor flexibility, impact resistance and color stability of phenolic resins have limited the scope of utility of such resins. In the field of coatings on various metallic and non-metallic surfaces, for example, coatings of phenolic resins, which have been formed by applying an organic solvent and curing to a hard, infusible state, are not only brittle but have poor adhesion to the surface to which they have been applied. Also, the use of phenolic based materials as laminating resins in electrical apparatus applications requires that they have a certain degree of flexibility and impact resistance in order to be useful in the preparation of cold punch stock.

Previous efforts to improve the properties of phenolic resins have been directed toward the use of various additives and plasticizers (modifiers) or by the use of various substituted phenols. These modified materials are economically unsuitable, and in many instances still have been known to have undesirable properties.

It is an object of this invention, therefore, to provide a flexible phenolic resin from an entirely different method than that used in the past.

It is a further object to provide a general purpose heterochain polymer which has a wide range of application in the fields of thermoset as well as thermoplastic resins.

Another object is to prepare a polymer which has both controllable flexibility and curability.

{another object is to prepare a polymer that is a base resin intermediate which can be used as such or reacted further to produce a flexible phenolic resin.

These and other related objects are achieved by the discovery of a flexible thermosetting polymer preparable in one reaction vessel by the method which comprises:

(1) Reacting a polymer containing an a,}8-carbon-tocarbon unsaturated carbonyl function with a nucleophilic compound having at least two active hydrogens, to form a polymer containing an active pendant nucleophilic group containing active hydrogen, and

(2) Reacting the resultant nucleophilic group containing active hydrogen on the said pendant group on the polymer with a compound selected from the group consisting of an aldehyde, a compound containing a C-methylol group, and mixtures thereof, and recovering the product so produced.

In step (2), when a compound containing a C-methylol group, that is, a resole, is the compound used, the result is the formation of a modified polymer containing pendant aralkylene groups, which is a non-heat curable resole or B-stage resin in which each successive nucleus is connected by a methylene group and/or oxymethylene (CH 0),,) linkages, which can be cured to a resite or a C-stage resin in which the cross-linking by electron bonds occurs and the product becomes infusible, yet is flexible.

In step (2), when an aldehyde is the compound used, the result is to form a polymer containing an active pendant methylol derivative group. This resultant polymer is a base resin intermediate which can be used as such or reacted further in accordance with steps (3) and (4) below to produce a flexible phenolic resin, as follows:

(3) Reacting the methylol derivative in the resultant polymer of step (2) with an aromatic compound containing an ortho-para activating group, to form a modified polymer containing a pendant aralkylene group containing at least one nuclear hydrogen capable of further condensation, and

(4) Reacting the resultant modified polymer of step (3) with an aldehyde to form a modified polymer con taining a pendant aralkylene polymer which is a resole or B-stage resin in which each successive nucleus is connected by a methylene group and/ or oxymethylene ((CH 0-) linkages which can be cured to a resite or a C-stage resin in which the cross-linking by electron bonds occurs and the product becomes infusible, yet is flexible.

As indicated above, each of the four reaction steps enumerated can be carried out in the same reaction vessel in sequence. Each step of the reactions of the process can be carefully followed by the use of conventional infrared analysis, by the more recent technique of attenuated total internal reflection (also known in the art as ATR) and by other quantitative titrametric analytical methods. Because of this, one of the especially remarkable aspects of this invention is that each step above enumerated can be varied individually to adjust the resultant desired polymer properties, such as flexibility and curability, so that almost any type of property or set of properties that is desired can be obtained by the use of this invention.

Nucleophilic addition (Step 1) In step (1), the preferred starting material polymers are polyesters containing a,p-carbon-to-carbon unsaturation, and are already defined in the literature. In addition to polyesters, the polymer containing an u,fl-carbon-to-carbon unsaturated carbonyl function can be formed from c punsaturated polycarbonyls (i.e., polyketones). Preferably the polyester is the reaction product of a polyhydric alcohol with an tap-unsaturated polycarboxylic compound.

The starting polymer for step (1) of this invention should preferably have a degree of polymerization of at least 3 (i.e., DP=3) and contain at least one a,,B-CaIbflto-carbon unsaturated carbonyl function. It is to be understood, however, that the polymer may have a degree of polymerization higher than 3, such as a DP of 100, and may have more than one a,,8-carbon-to-carbon unsaturated carbonyl function. They can be prepared with various properties by varying the ratio of the difunctional compounds containing the unsaturated and saturated linkages. In this way, polyesters of varying properties can be obtained. Since the bridging or condensation of the polyester with the phenolic resin will take place at the nucleophilic center attached to the u,;8-carbon-to-carbon unsaturation, the amount of bridging or cross-linking sites that are desirable in any given polymer can be varied by varying the amount of unsaturated acid which is used in the polyester. In general, it can be said that if one uses one mole of an anhydride there must be one mole of glycol present to react with it. Essentially, the mole ratio of acid monomer to alcohol monomer should be between about 1:1 and 1: 1.5 on a molar basis.

The acids which may be used to prepare the polyester of step (1) in my process may be from among any of those known in the art which are known as anhydrides, half-esters, dicarboxylic acids, acid chlorides, and w-hydroxy acids, as well as w-mercapto acids. The polyester monomer should contain a known amount of 0:,[3-62111301'1- to-carbon unsaturation adjacent the carboxyl group. The polyester may also contain saturated acid moieties as well, to adjust the ratio of unsaturation to polymer length.

Examples of unsaturated anhydrides which may be used to form the polyester of step (1) are: maleic, chloromaleic, alkylmaleic containing from one to 18 carbon atoms, such as ethylmaleic, itaconic, citraconic, zeronic, pyrococinchoninic and acetylene dicarboxylic, either alone or in mixtures.

Among the unsaturated half-esters which can be used in the preparation of the polyester of this invention are: fi-carboalkoxy acrylic acid of one to 18 carbon atoms, such as fl-carbomethoxy acrylic acid, and B-carboethoxy acrylic acid, the alcoholated, the aminolated, and the thiolated products of the above-mentioned unsaturated anhydrides.

Among the unsaturated dicarboxylic acids and acid chlorides which can be used in the preparation of the polyester of step (1) of this invention are: maleic acid, fumaric, itaconic, citraconic, mesaconic, glutaconic and alkyl glutaconic of one to 18 carbon atoms, acetylene dicarboxylic acid, chloromaleic acid, chlorofumaric acid, bromomaleic acid, fiuoromaleic acid, and the like.

Among the unsaturated w-hydroxy acids which may be used to prepare the polyester of step (1) of this invention: wy-diethyl 'y hydroxycrotonic acid, p-hydroxyacrylic acid, fi-alkyl hydroxyacrylic acid of one to 18 carbon atoms, such as B-hydroxyalkyl acrylic acid.

Among the w-mercap-to unsaturated carboxylic acids which may be used to prepare the polyester of step (1) of this invention are: wy-diethyl-v-mercaptocrotonic acid, fl-mercaptoacrylic acid, [i-alkylmercapto acrylic acid of one to 18 carbon atoms, such as B-mercaptoethyl acrylic acid. p-alkylmercapto acrylic acid of one to 18 carbon atoms, such as fl-mercaptoethyl acrylic acid.

As mentioned above, the polyester of step (1) may also be prepared from a mixture of unsaturated dicarboxylic acids with saturated dicarboxylic compounds which are well known in the art and can include: glutaric acid, succinic acid, adipic acid, sebacic acid, dicarboxylic acids of one to 18 carbon atoms, alkylene of six to sixty carbon atoms, alkyl dimeric acids, halogenated dicarboxylic acids, such as hexachloroglutaric acid and hexafluoroglutaric acid, aromatic dicarboxylic acids, such as phthalic acid and anhydride, terephthalic acid and isophthalic acid and alicyclic dicarboxylic acids and anhydrides, such as chlorendic anhydride.

In addition, the polyester of step (1) of the above process is formed from a hydroxy compound which is also well known in the art. Examples of such hydroxy compounds are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyglycol, butane diol, pentane diol, hexane diol, glycerol, mannitol, sorbitol, hydrogenated bisphenols, alkene diols of four to 18 carbon atoms, such as butene diol, pentene diol, hexene diol, oxyalkylated bisphenols of one to 18 carbon atoms, such as oxyethylated and oxypropylated bisphenols, substituted oxyalkylated bisphenols of one to 18 carbon atoms and substituted with halogens selected from chlorine, bromine, fluorine, and the like, bisoxyalkylated hydroxyphenyl sulfones, such as bisoxyethylated and bisoxypropylated hydroxyphenyl sulfones, oxyalkylated polymethylene bisphenols where the polymethylene group has from two to 18 carbon atoms and the oxyalkylation groups have from two to three carbon atoms, and mixtures thereof.

Th ratio of unsaturated acid to saturated acid used to form the polyester of step (1) of this method can be varied within wide limits, depending on the ultimate properties desired in the flexible phenolic resin. Also, the nature of the hydroxy compound used in the polyester should be taken into consideration with the saturated acid aspect of the resulting polyester. In an approximate sense, the saturated acid portion of the polyester can be considered with the saturated glycol portion of the polyester as imparting flexibility and stability to the ultimately desired flexible phenolic resin. The polyester resins of the above description are already well known in the polyester art and in general impart two desirable characteristics to the resultant flexible phenolic polymer:

(a) They give active unsaturated sites which can be used to chemically modify the polymer by having attached to it active pendant functional groups.

(b) The polyester linkage may also provide the flexibility and stability to the resultant polymer.

Step (1) of my process, on the nucleophilic addition of an active hydrogen compound to the a,fl-unsaturated carbon-to-carbon double bond, is illustrated by Equation 1:

where R XH' is a nucleophile in which the hetero atom, X, is nitrogen, oxygen, phosphorus, sulfur, arsenic, boron, and the like, and R is as defined below.

Where the nucleophilic compound contains nitrogen, the compound must be a primary amine in order to provide an active pendant group for the subsequent modications. Among the hetero nitrogen nucleophilic compounds which may be used are cyanamide (H2NCEN) ammonia, 2,4,6-triaminophenol, phenylhydrazine, hydrazine, hydrazine-hydrochloride, urea, N-phenylhydroxylamine benzaldehyde oxime, Z-methylpyrrole 2,3-din1ethylpyra2ines, carbamyl azide i ulN 0 -N\ diazamethane (CH N ),dicyanodiamide, guanidine Nll UNlI -U-Nll 2-zimino-2methyl-1,3-propanedio1, and the like.

Other examples of compounds containing nitrogen hetero groups are thiourea, lower alkanol amines of two to 18 carbon atoms, such as ethanolamine, lower alkylamines of one to 20 carbon atoms, such as methylamine, ethylamine, propylamine, butylamine, amylamine, dodecylamine, hexamethylenetetramine and tallowamine, alicyclic amines from five to 20 carbon atoms, such as cyclohexylamine and cycloheptylamine, aniline, substituted anilines wherein the substituents may be hydrogen, alkyl of one to 20 carbon atoms, aryl from six to 20* carbon atoms, halogens selected from chlorine, fluorine, bromine and iodine, hydroxy, sulfonyl sulfone (:8O- sulfate (-50,), sulfonic (SO H), Phosphate (--PO phosphites (-PO H), nitro, nitroso and alkoxy from one to 20 carbon atoms.

Where the nucleophilic compound contains oxygen, each oxygen has only one hydrogen bonded to it which can undergo nucleophilic addition. The second active hydrogen can be supplied in the compound through a second oxygen or some other hetero atom in the compound, such as phosphorus, sulfur or nitrogen. In this case, the phosphorus, sulfur or nitrogen compound has at least one additional active hydrogen in the molecule. An exception to this is the case of water (H O) which does not react in this way and is not included within the scope of this definition.

Among the hetero oxygen nucleophilic compounds which may be used are: oximes such as benzaldehyde oxirne, glycols such as ethylene glycol and propylene glycol, hydrogen peroxide (H hydroquinone, 2,6-dihydroxymethyl phenol, oxyalkylated bisphenol of 1 to 18 carbon atoms such as oxyethylated bisphenol, 2,4,6-triarninopheno1, N-hydroxymethylcyanamide H HO-CHz-fiF-ON) and the like.

Where the nucleophilic compound contains phosphorus, the phosphorus can be in either the trior pentavalent state. The two active hydrogens can be either directly bonded to the phosphorus, such as in alkyl phosphines containing one to 18 carbon atoms, or indirectly bonded to the phosphorus through other hetero atoms, such as nitrogen, sulfur and oxygen. Among the hetero phosphorus nucleophilic compounds that may be used are: tris-hydroxymethylphosphine, methylphosphonic acid, phosphine, bis(hydroxymethyl)phosphinic acid (BHMP) methyl acid phosphate butyl acid phosphates, and the like.

Other examples of compounds containing phosphorus hetero groups are alkyl phosphines (RPH of one to 20 carbon atoms, such as methylphosphine, ethylphosphine, propylphosphine, butyland decylphosphine, dodecylphosphine, and stearylphosphine, phosphonic acid.

alkyl phosphonic acid where the alkyl has from one to 18 carbon atoms and alkyl phosphorus amides of from one to 18 carbon atoms, such as N-methyl phosphorus amide.

Where the nucleophilic compounds contains sulfur, the sulfur can be in any of its multivalent states. The two active hydrogens can be either directly bonded to the sulfur, such as in hydrogen sulfide, or indirectly bonded to the sulfur through other hetero atoms, such as nitrogen, oxygen, phosphorus or other sulfur. In the case where the nucleophilic compound is hydrogen sulfide (H 8), then R is zero.

Among the hetero sulfur nucleophilic compounds which may be used are: thiourea (his...)

acetonethiosemicarbazone thiosulfuric acid p-aminobenzenethiol (H NC H SH), hydrogen sulfide (H 8), 2-thioethanol (HO-CH -CH SH), and the like.

Compounds containing hetero atoms of arsenic and boron may also be used. Examples of such hetero arsenic compounds are tris-hydroxymethyl arsine, methylarsonic acid, arsine, bis(hydroxymethyl)arsinic acid, methyl acid arsenate, butyl acid arsenate, alkyl arsines (RAsH of one to 20 carbon atoms, such as methylarsine, ethylarsine, propylarsine, butylarsine, dodecylarsine and stearylarsine. When using an arsine such as tris-hydroxymethyl arsine, the nucleophilic reaction would be conducted in a manner after Example 5 below.

Examples of such hetero boron compounds are boric acid (B(OH) metaboric acid, diborane (B H triborane (B H tetraborane (B H pentaborane (B H and B H hexaborane B H and B H enneaborane (B H and B H decaborane (B H and B H as well as derivatives of boron with nitrogen such as borazole and with phosphorus such as the compound having empirical formula B P C H and the cyclic structure When using diborane, the nucleophilic reaction would be conducted in a manner after Example 2 below. And, when using borazole, the nucleophilic reaction would be conducted in a manner after Example 1.

The R in the Equation 1 can be hydrogen, lower alkyl containing from one to 18 carbon atoms, substituted alkyl, aryl containing from 6 to 20 carbon atoms, substituted aryl, alicyclic containing from 4 to 20 carbon atoms, carbamidoyl and thioamidoyl, n is zero or one.

The alkyl groups in R can have from one to 18 carbon atoms. The substituents on the substituted alkyl groups can be hydrogen, lower alkyl of one to 18 carbon atoms, halogens selected from chlorine, fluorine, bromine, iodine and aryl of six to 20 carbon atoms.

The substituents on the substituted aryl groups can be hydrogen, alkyl of one to 18 carbon atoms, halogens selected from chlorine, fluorine, bromine and iodine, aryl of six to 20 carbon atoms, sulfone (=SO sulfonic (-SO H), nitro, nitroso, hydroxy, alkoxy of one to 18 carbon atoms.

Examples of aryl groups are phenyl, naphthyl, toluyl and the like.

Examples of alicyclic compounds are cyclohexyl, Decalin, Tetralin, cycloheptyl, cyclopentyl, bicyclic compounds such as norborinyl and the like.

The nucleophile (R XH to be used depends on the desired properties of the ultimate product.

It is important that the mole ratio of the nucleophilic compound to the molar amount of a,;8-unsaturation in the polymer be at least about 1:1. If less than the molar equivalent of unsaturation is added, then there remains in the polymer some unreacted double bonded material. Under this condition, the resultant adduct undergoes secondary addition with the excess unsaturated portion of the remaining polymer; thus reducing available active sites for the subsequent reaction. If a molar excess of nucleophilic compound is added, this excess remains in the mixture and may react preferentially with the subsequently added reagents.

The reaction can be followed by use of various known titrametric analytical methods, as well as by infrared analysis and by attenuated total internal reflection (ATR) analysis.

The temperature to be used in carrying out the nucleophilic addition step will vary with the nature of the unsaturated polymer and with the activity of the nucleophilic agent. In general, however, this temperature range is between about zero degrees centigrade and about 250 degrees centigrade. The preferred temperature range is between about 50 degrees centigrade and about 150 degrees centigrade. At temperatures above the maximum temperature, a retrograde reaction may result, because the reaction can be reversed by thermal induction. At temperatures below the minimum temperature, the reaction tends to become sluggish.

The reaction is carried out under generally basic conditions, i.e., at a pH greater than 7. Under acid conditions, with amines, for example, ammonium salts are formed which do not react satisfactorily.

Methylolation (step 2) Regarding step (2) on the methylolation of the active hydrogen on the pendant group attached to the polymer, this is illustrated by Equation 2:

where R and X are as defined above.

While the equation above uses formaldehyde to illustrate the reaction, it is to be understood that any aldehyde reactive with nucleophilic hydrogen may be used in this invention. Examples of aldehydes to be embraced within the scope of this invention are formaldehyde, including paraformaldehyde and trioxane, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, furfural, Z-ethylhexanal, ethylbutyraldehyde, heptaldehyde, dialdehydes, such as glyoxal, aldols, such as hydroxy acetaldehyde, crotonaldehyde, acrolein, halogenated aldehydes where the halogens are chosen from chlorine, fluorine, bromine and iodine.

In general, the aldehyde must be capable of reacting with the reactive hydrogen on the pendant group attached to the polymer. The aldehyde can contain from one to 18 or more carbon atoms and may be substituted with other groups which do not interfere with the nucleophilic addition reaction or with subsequent reactions in steps (3) and (4). The preferred aldehyde to be used Will depend upon the desired properties in the ultimate polymer.

When the aldehyde used is formaldehyde, the methyl group is unsubstituted, whereas when some other aldehyde is used the methyl group can be considered to be substituted with an alkyl or aryl substituent. For instance,

tion 3:

II II K'EH-CHZ-C cu o ewcn c XH X 2 D HO-Cf CHZOH where X is as defined above.

This type of reaction is dependent largely upon the stoichiometry of the reactants.

It is important that the mole ratio of the aldehyde to the reactive hydrogen on the pendant polymer chain be at least about 1:1. If less than the molar equivalent of aldehyde is used, then cross-linking may occur between the remaining active hydrogen and the resultant methylol pendant groups to form, for instance, -amino-methy1- arnino- (NCH N bonding. This reduces the number of pendant groups that are available for the sub sequent reaction (step (3)). If a molar excess of aldehyde is used, this excess remains in the mixture without harm.

The temperature to be used during the reaction Will again depend upon the nature of the polymer and its pendant reactive hydrogen reactivity, as well as the nature X-methylation of aromatic compounds (step 3) After the pendant group on the polymer has been reacted with an aldehyde in step (3), the resultant methylol pendant group is then reacted at a temperature from about zero to 200 C. with an aromatic compound containing an ortho-para activating group to produce a pendant novolac, as illustrated by Equation 4:

where X is as defined above, and R is as defined above.

The types of novolacs to be embraced within the scope of this invention are those chosen from phenols, phenolic novolacs, substituted phenols, thiophenols, aniline type compounds and aniline formaldehyde novolacs.

Examples of phenols which may be used in preparing the novolac of this step include phenol itself and substituted phenols having the following general formula:

where Y may be H, F, Cl, Br, I, or a suitable substituent selected from the following:

(a) Alkyl groups of one to 18 carbon atoms in any of their isomeric forms and substituted on the phenolic nucleus in the ortho, or para positions;

(b) Alicyclic groups of to 18 carbon atoms such as cyclohexyl, cyclopentyl, methyl cyclohexyl, butyl cyclohexyl, etc.;

(0) Aromatic or aralkyl groups of 6 to 18 carbon atoms such as phenyl, hydroxyphenyl, alpha-methylbenzyl, benzyl, cumyl, etc.;

((1) Novolac groups. having the formula:

e -(e l where n is one to ten.

Suitable substituted phenols include the following:

para-tertiary-butylphenol, para-secondary-butylphenol, para-tertiary-amylphenol, para-secondary-amylphenol, para-tertiary-hexylphenol, para-isooctyl-phenol, para-phenylphenol, para-benzylphenol, para-cyclohexylphenol, para-decyl-phenol, para-dodecyl-phenol, para-tetra-decyl-phenol, para-octa-decyl-phenol, para-nonyl-phenol, para-methyl-phenol, para-beta-naphthyl-phenol, para-alpha-naphthyl-phenol, para-pentadecyl-phenol, para-cetyl-phenol, para-cumyl-phenol, para-hydroxy acetophenone, para-hydroxy benzophenone,

a phenol reacted or alkylated with limonene in any of its isometric d-, l-, or dlforms, a phenol alkylated with styrene, a phenol alkylated with pinene in any of its isomeric a or [3 forms, as well as the corresponding ortho and meta derivatives such as meta-butyl phenol and orthobutyl phenol, as well as mixtures thereof.

From the foregoing, it is apparent that substantially any phenol may be used in practicing step (3) of the present invention provided it has a reactive phenolic hydroxyl group and is capable of reacting with the hydroxy methyl group pending from the polymer, and does not have reactive functional groups which interfere with the condensation reaction. The pure refined phenols may be used, but this is not always necessary. For instance, phenols may be alkylated and then reacted with an aldehyde as the crude product which may contain some polyalkylated as well as unalkylated phenols. Mixtures of phenols mentioned may also be used.

Examples of thiophenol compounds or substituted thio phenol compound which may be used in this step are illustrated as follows: thiophenol =(mercapto phenol), sulfur phenol novolae of the formula:

six to 20 carbon atoms, amine (-NH hydroxy, mercapto, aniline formaldehyde novolacs of the formula:

2 Don where n is one to ten.

The ratio of the phenolic type compound to the methylol groups pending from the polymer may vary from 1:1 to infinity to 1, depending on the properties of the end product desired.

In those instances Where the pendant group attached to the polymer has been reacted with the compound yielding two available hydrogens for reaction with the aldehyde, when the phenolic compound is then reacted with it, it is capable of obtaining a mixed product illustrated by Equation 5:

where X is as defined above.

If an excess of the phenolic compound is used over that required for the reaction with the one methylol group on the pendant group, then it is possible to also react the second hydroxymethyl group.

In step (2), when a compound containing a C-methylol group, that is, a resole, is the compound used, the result is the formation of a modified polymer containing pendant methylolated aralkylene groups, which is a non-heat curable resole or Bstage resin in which each successive nucleus is connected by a methylene group and/or oxymethylene ((CH O) linkages, which can be cured to a resite or a C-stage resin in which the cross-linking by electron bonds occurs and the product becomes infusible, yet is flexible. And when an aldehyde is the compound used in step (2), the result is to form a polymer containing an active pendant methylol derivative group. This resultant polymer is a base resin intermediate which can be used as such or reacted further in accordance with steps (3) and (4) to produce a flexible phenolic resin. This illustrates the diversity of the processes of this invention in that either a base resin may be prepared (by the use of appropriate aldehydes in step (2), for example) which can be further modified later as convenient, or, any of a number of finished products may be directly prepared by the use of the appropriate reactants.

'Methylolation of aromatic compound (formation of the flexible resin) (step 4) After the modified polymer containing an active pendant alkyl aromatic group containing active nucleohydrogen of step (3) has been prepared, the next step is to add a compound selected from the group consisting of an aldehyde, a compound containing a C-methylol group, and mixtures thereof, to the resulting novolac to form a flexible thermosettable polymer containing a hetero pendant group on which is an aromatic C-methylol group. This reaction is illustrated by Equation 6:

@23 on I Ch UH where R and X are as defined above.

Where the nucleophilic addition compound has two active hydrogen groups available after it has become attached to the polymer group (i.e., where R is hydrogen), then the resultant thermosettable phenolic compound obtained from this reaction would contain both a C-methylol group and an X-methylol group, and would appear as illustrated in Equation 7:

CH OH where X is as defined above.

As with step (2) on the methylolation, likewise with this step, any suitable aldehyde or mixtures of aldehydes capable of reacting with reactive hydrogen or ortho-para activated ring hydrogen to form a hydroxylmethyl group or methylol derivatives having not more than, for example, eight carbon atoms, is satisfactory for effecting the process of this invention, provided it does not contain a functional group or structure which is detrimental to the reaction. The preferred aldehyde is formaldehyde, how ever, this will be dependent upon the ultimately desired properties of the flexible phenolic resin. The formaldehyde may be an aqueous solution or in any of its low polymeric forms such as paraform or trioxane. Other aldehydes named above may also be used.

The ratio of the aldehyde to the novolac of step (3) may be varied within a wide range depending on the desired properties of the ultimate end product.

The temperature to be used in effecting this reaction of step (4) may vary between about zero degrees centigrade and about 200 degrees centigrade. At temperatures below zero degrees centigrade, the reaction may be sluggish. At temperatures above 200 degrees centigrade, the reaction may go beyond the C stage. The preferred temperature is between about 30 degrees centigrade and about 100 degrees centigrade.

Each of the steps illustrated above can be carried out as separate reactions, that is, in separate reaction vessels. However, it is one of the unique discoveries of this invention that each step can be carried out in a single reaction vessel in sequence. Another discovery is that the reaction product can be isolated and used accordingly, at any stage. The steps need not be carried out simultaneously but can be interrupted at any stage and re-initiated at a later date. Where the desired reaction product of step l) is already available on the market, then the reaction of step (1) has already been carried out, and my process can be proceeded with from step (2). Likewise, where the desired compound of step (2) is already available on the market, the reactions of steps 1) and (2) have already been carried out, and I would proceed with my process at step (3). i

The flexible phenolic base resins of this invention are useful for a multitude of purposes, including interior 12 can coatings, drum and pail linings, wire coatings, laminating resins (cold punching), baking primers, adhesives, pipe coatings, reactive plasticizers and diluents, phenolic molding resins, foundry resins, grinding wheel binders, rubber tackifiers, paper coatings, textile treatments, and the like.

The invention is further illustrated in the following illustrative examples which are given for purposes of illustration only and are not to be construed as limiting except as defined in the appended claims. Unless otherwise indicated, all parts are by Weight and temperatures are in degrees centigrade.

In Section I, unsaturated polyesters (polymaleates) were prepared by reacting maleic anhydride and a slight molar excess of difunctional alcohols. To these unsaturated polyesters, Michael addition of amine were carried out in the subsequent examples, to give polyamino esters. The resultant polyamino esters were then reacted with formaldehyde to give N-rnethylolated polyamino esters which further reacted with phenol and formaldehyde to give hetero chain polyesters.

( I POLYMALEATES Preparation of poly(oxytriethylene)maleates- Method A A one liter three-necked flask is equipped with a stirrer, thermometer and condenser with a Dean-Stark water separator set for the azeotropic distillations. In a flask is placed 98.06 parts (one mole) of maleic anhydried, 190.17 parts (1.25 moles) of triethylene glycol and 250 milliliters of dry toluene and one gram of p-toluenesulfonic acid. The mixture is refluxed until one mole of water is collected. The solvent is removed under reduced pressure to give a clear, light yellow unsaturated polyester of molecular weight between 1500-1800.

Method B A one liter three-necked flask is equipped with a stirrer, siphon, nitrogen inlet and thermometer (all reaching below the surface of the solution) and a side arm with condenser set for distillation. In the flask is placed 332 parts (2.2 moles) of triethylene glycol, which is heated to degrees centigrade, after which 196 parts (2 moles) of maleic anhydride are added. The temperature is raised to degrees centigrade over a one hour period, then raised to degrees centigrade and held for four hours with sub-surface nitrogen bubbling into the reaction mixture. Then, vacuum was applied, until the acid number of a sample was less than 10 milligrams of KOH per gram of sample. The polyester prepared in such a manner was light yellow in color and its molecular weight ranged from 1300 to 4500.

(II) NUCLEOPHILIC ADDITION Example 1.Preparation of poly[ 3(N phenylamino)- oxytriethylene]succinate by reaction of unsaturated polyester with aniline To a reaction flask containing 250 parts of the poly (oxytriethylene)rnaleate prepared by Method A were added 500 parts of l-butanol. To this 93.12 parts (one mole) of freshly distilled aniline were added over a period of two hours, under the refluxing temperature of l-butanol. At the end of four hours of reaction time a sample was withdrawn and analyzed for free aniline by non-aqueous titration using 0.1 Normal perchloric acid. At the end of eight hours, 98 percent of the aniline was reacted. The resultant product, poly[fi(N-phenylamino) oxytriethylene]succinate, is soluble in most of the common organic solvents and insoluble in water.

Example 2.-Preparation of [(B-amino)oxytriethylene] succinate by reaction of unsaturated polyester with alcoholic ammonia To a reaction flask containing 240 parts of poly(oxytriethylene)maleate prepared by Method B were added 250 parts of absolute ethanol. To this were added 500 parts of absolute ethanol, conjoining 17.5 parts of dissolved ammonia, at a temperature of zero degrees centigrade over a period of two hours. After the completion of addition, the reaction mixture was allowed to reach room temperature for an additional two hours. A sample was Withdrawn and analyzed as in Example 1. The resultant product, poly[ (fl-amino)xytriethylene1succinate, is soluble in water.

Example 3.Preparation of poly[B-(0,0'-dimethylolphenoxy)oxytriethy1ene]succinate by reaction of unsaturated polyester with 0,0'-dihyd.roxyrnethylphenol Using 230 parts of unsaturated polyester prepared by Method A, 500 parts of toluene as a solvent and 123 parts of 0,0'-dihydroxymethylphenol as a nucleophilic substance, and the method of Example 1, the above polymer is produced. It is soluble in toluene and alcohols and insoluble in water.

Example 4.-Preparation of poly[B-(Z-thio-pseudourea) oxytriethylene1succinate by reaction of unsaturated polyester with thiourea Using 230 parts of unsaturated polyester prepared by Method B, 500 parts of l-butanol as a solvent and 76.12 parts (one mole) of thiourea, and the method of Example 1, the above polymer is produced. The polymer is partly soluble in water.

Example 5.Preparation of polyw-ethylhydrogenphosphinyl]-oxytriethylene succinate To a reaction flask containing 230 parts of unsaturated polyester prepared by Method A are added 94 parts of ethyldihydrogen phosphinate (C H P(O)H at a temperature of about 30 degrees centigrade over a period of about two hours. The resultant polymer is analyzed for phosphorus and is soluble in water.

(III) METHYLATION Example 6.-Preparation of polyUS-(N-phenyl-N-hydroxymethyl)oxytriethylenejsuccinate by reaction of polymer of Example 1 with aqueous formaldehyde To a reaction flask containing 350 parts of the polymer of Example 1, 85 parts (one mole) of 37 percent aqueous formaldehyde were added dropwise over a period of two hours at the temperature of 50 degrees centigrade. After the completion of addition of formaldehyde, the reaction mixture was stirred an additional two hours. The resulting reaction mixture was subjected to dehydration under reduced pressure at a temperature of 30 degrees centigrade to give the above polymer as a viscous liquid. A sample was withdrawn and subjected to infrared spectroscopy and found to contain N-methylol functionals. The resultant polymer, defined above, is soluble in most of the common organic solvents and insoluble in water.

Example 7.-Preparation of polym-(N-phenyl-N-hydroxymethyl)oxytriethylene succinate] by reaction of polymer of Example 1 with anhydrous paraformaldehyde The above polymer was prepared in a manner after Example 6, except that 13 parts (one mole) of paraformaldehyde were used instead of the 37 percent aqueous formaldehyde, and 500 parts of l-butanol were used as a solvent, and the reaction conducted at the refluxing temperature of the l-butanol. After about four hours the solvent was removed under reduced pressure at a temperature of 30 degrees centigrade to give the above polymer as a viscous liquid. A sample was analyzed as in Example 6 and found to contain N-methylol functionals. The polymer is also soluble in most common organic solvents and insoluble in water.

When trioxane is substituted for paraformaldehyde in Example 7, the same polymer is produced as obtained in Example 7.

Example 8 When the polymer of Example 4 is reacted with paraformaldehyde in a manner after Example 7, the pendant 2-thio-pseudourea group on the polymer is methylolated.

Example 9 When the polymer of Example 5 is reacted with paraformaldehyde in a manner after Example 7, the pendant phosphinyl group on the polymer is methylolated to a hydroxymethylethylphosphinyl pendant group.

(IV) NOVOLAC PREPARATION Example 10.-Preparation of polyUS-(N-phenyl-N- hydroxybenzyl) oxytriethylene] succinate To a reaction flask containing 430 parts of the polymer of Example 6 were added 94 parts of phenol (one mole). The reaction mixture was subjected to dehydration under reduced pressure at the temperature of 75-85 degrees centigrade for three hours to give a very viscous resin. A sample was withdrawn and the hydroxyl number was determined to be poly(amino methylated) phenol defined above.

Example 11 When the modified polymer of Example 8 is reacted with phenol in a manner after Example 10, the pendant 2-thio-pseudourea group is alkylated to phenol through methylol functionals. This can be subsequently reacted with an aldehyde to give a C-methylolated novolac which can be cured thermally. Or it can be cured to the infusible state with hexamethylenetetramine. Or it can be cured with a resole.

Example 12 When the modified polymer of Example 9 is reacted with phenol in a manner after Example 10, the pendant hydroxymethylethylphosphinyl group is alkylated to phenol through methylol (i.e., hydroxymethyl) functionals. This likewise can be subsequently cured to the infusible state by known methods, such as those mentioned in Example 11.

Example 13.Reaction of poly[p-(N-phenyl-N-hydroxymethyl)oxytriethylene]succinate with phenolic novolac To a reaction flask containing 200 parts of the modified polymer of Example 6 were added 200 parts of a commercial phenolic novolac resin known in the trade as Durez #10 Resin, and reacted in a manner after Example 10, to give the low melting solid described above, which can be subsequently cured such as with hexamethylenetetramine to an infusible yet flexible resin.

Example l4.Reaction of poly[fi-(N-phenyl-N-hydroxylmethyl)oxytriethylene] succinate with sulfur novolac To a reaction flask containing 200 parts of a modified polymer of Example 6 were added 200 parts of a sulfur novolac made in accordance with U.S. Pat. No. 3,409,676 and reacted in a manner after Example 10, to give the low melting semi-solid resin described above. This can be cured with hexamethylenetetramine to an infusible yet flexible resin.

Example 15 .-Poly (N-methylol-N-phenyl polyglycol succinate gradually heated under nitrogen and when the temperature reached 190 degrees centigrade, an exotherm started. All the heat was turned off. The exotherm reached 215 degrees centigrade and lasted for about 30 minutes. The reflux vapors were carried through a packed column to a condenser for better separation of water and glycol. At the end of about 3.5 hours of reaction, 1.5 parts of distillate were collected. The distillates were analyzed for glycol and shown to contain about seven percent of glycol by the refractive index method.

The reaction mixture was cooled to about 85 degrees centigrade and samples for acid number were withdrawn. At the end of 3.5 hours of reaction, the acid number was 45.50 milligrams of KOH per gram of sample.

At the end of 9.5 hours of total reaction time the acid number reached 20.00 milligrams of KOH per gram of sample and the reaction mixture became very viscous even at 180 degrees centigrade. At this point, dehydration was terminated and the reaction mixture was cooled to 80 degrees centigrade.

To this mixture 88 parts of n-butanol were added and then 27.79 parts of aniline were added. The reaction temperature was raised to the refluxing temperature of n-butanol, namely, about 1120 degrees centigrade, A sample was withdrawn at the end of ten hours of reflux and analyzed for free aniline, and showed 89 percent of the aniline was reacted and 11 percent unreacted aniline remained. The reaction was refluxed for an additional three hours to bring the total unreacted aniline to five percent and at this point 951 parts of solid paraformaldehyde (of 96 percent pure material) were added. Periodically samples were withdrawn and examined for paraformaldehyde consumption. The resin was discharged into four containers. The yield was 140 parts of finished resin. This resin, having pendant N-methylol groups, can be subsequently utilized such as illustrated in Example 10.

The final product of Example :15 can be used in the formation of laminating resins, illustrated in Table I:

TABLE I Laminating resin formulation Material: Parts Product of Example 15 280 Resole (e.g., an A-stage phenolic resin) 250 Example 1 6 To 460 parts of poly(N-methylolN-phenyl)polyglycol succinate of Example 15 were added 282 parts (3.0 moles) of phenol, an additional 47.8 parts (1.5 moles) of paraformaldehyde, 8 parts (0.05 mole) of tartaric acid and 20 milliliters of water. The reaction temperature was maintained at d-1l0 degrees centigrade :for one to two hours. Then the product was dehydrated to 160 degrees centigrade pot temperature at 10-15 millimeters mercury during a period of about two hours. The final product, poly(N phenyl-N-hydroxybenzyl)aminopolyglycol succinate, is a base resin which can be used as a multipurpose base resin. It can be further cross-linked in known ways, as explained in Example :11.

The final product of :Example 16 can be used as reactive diluent for commercially available polyesters and also phenolic novolacs.

The afinal product of Example 16 can be used in a typical molding resin formulation shown in Table II:

TABLE II Molding resin formulation Material: Parts Base resin of Example 16 222.0 Formalin (37 percent) 120.0 INaOH (anhydrous) 2.8 Formic acid (85 percent) 2.1

Example l7.-Preparation of a flexible phenolic resin from poly 8- (N-phenylamino oxytriethylene] succinate and a resole To a flask equipped with stirrer and thermometer were added 250 parts of poly[B-(N-phenylamino)oxytriethylcne]succinate made in accordance with Example 1, 200 parts of a commercially available resole (an A-stage phenolic resin), and 2 parts of sulfuric acid. The resulting mixture was stirred at room temperature for two hours to give a homogeneous mixture. The resulting product was dehydrated under reduced pressure at a temperature of about 50 degrees centigrade to give a light brown viscous resin which can be further cross-linked with hexamethylenetetramine or a resole to give infusible and insoluble, yet flexible material.

Example :18.Preparation of -N-su=bstituted polyaminoester modified flexible phenolic resins To a three-necked flask, fitted with a thermometer, mechanical stirrer, inert gas sparge and a water removal apparatus fitted with a condenser were added 116 parts (1.20 moles) of maleic anhydride, 300 parts (1.0 mole) of polyethylene glycol having a molecular weight of about 300, and 42.5 parts (0.4 mole) of diethylene glycol. The mixture was heated under a nitrogen blanket to 200-220 degrees centigrade and held until an acid number of 510 milligrams of KOH per milligram of sample was obtained. It was cooled to degrees centigrade and then 221 parts (3 moles) of n-butanol were added. While stirring, parts (1.13 moles) of aniline were added over a two hour period under n-butanol reflux. Heating was continued until more than 90 percent of the unsaturation had been reacted out.

After stripping off the n-butanol (98 percent recovery) and adding 235 parts (25 moles) of phenol and 243 parts (3 moles) of 37 percent formalin, the mixture was stirred at 60-70 degrees centigrade for 24 hours.

The water was stripped off at reduced pressure with an aspirator and dehydration continued up to degrees centigrade until the theoretical amount of water was collected.

The product had the properties shown in Table III:

TAB-LE III Physical properties of polyaminoester modified Eflexible phenolics State Viscous liquid. Color Light brown. Percent N 2.l44.2 percent. Hydroxyl number 204559 Acid number 5-20.** :Molecular weight (MW) 4'00'-300'0. Viscosity 15-90 (stokes). Non-volatile 98 percentf' Transparency Good. Total percent aminoester backbone in resin 25-50 percent.

*2 percent of volatile consists of formaldehyde and solvent.

f*Acid number determined on the unsaturated polyester prior to reaction with aniline.

Films were made from the product whose properties are described in Table III, by diluting with ethanol to spraya ble viscosity. No additives or flow controlling agents were used. The resins were coated on standard Q panels, tin can stocks by means of a blade applicator (ASTM D-1436) and cured in a draft oven at degrees centigrade for 30 minutes. Flexibility was checked with a conical mandrel over 4; inch diameter, and in the case of can stocks, bent into two degree folds made at right angles (approximate) and the sharp edge examined. In all cases the film passed these standard tests with a rating of excellent.

Various changes and modifications may be made in the method and compositions of this invention, certain preferred forms of which have been herein described,

17 without departing from the spirit and scope of this invention. These modifications in this basic invention are to be regarded as within the scope and purview of this invention.

For instance, where a polymer is already available which contains an active pendant nucleophilic group containing at least one active hydrogen, then the method of this invention can be carried forward beginning with step (2). Examples of such known polymers are polyaspartic acid, poly(3,5 octamethylene 4amino-1,2,4-triazole), polyacrylamide oxime, polyvinyl alcohol and the like.

I claim:

1. A method which comprises:

(1) reacting a polymer containing an alpha,beta-carbon-to-carbon unsaturated carbonyl function with a nucleophilic compound having at least two active hydrogens which has the empirical formula R XH wherein X is selected from at least one of nitrogen, phosphorus, sulfur, oxygen, arsenic, and boron; n is or 1 and R represents at least one radical selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alicyclic, carbamidoyl and thioamidoyl, at a temperature from about 0 C. to about 250 C. to form a polymer containing an active pendant nucleophilic group containing at least one active hydrogen,

(2) reacting the resultant nucleophilic group containing active hydrogen on said polymer with a compound selected from the group consisting of an aldehyde, a compound containing a C-methylol group and mixtures thereof at a temperature of about 0 to 175 C.

2. The method of claim 1 wherein the molar amount of nucleophilic compound in step (1) is substantially equivalent to the molar amount of alpha,beta unsaturation in the polymer.

3. The method of claim 1 wherein the reaction of step (1) is carried out at a pH greater than 7.

4. The method of claim 1 wherein the two steps are carried out in sequence in the same reaction vessel.

5. A polymer produced by the method which comprises reacting a polymer containing an alpha,beta-carbon-tocarbon unsaturated carbonyl function with a nucleophilic compound having at least two active hydrogens which has the empirical formula R XH wherein X is selected from at least one of nitrogen, phosphorus, sulfur, oxygen, arsenic, and boron; n is 0 or 1 and R represents at least one radical selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alicyclic, carbamidoyl and thioamidoyl, to form a polymer containing an active pendant nucleophilic group containing at least one active hydrogen, and reacting the re sulting nucleophilic group containing active hydrogen on said polymer with a compound selected from the group consisting of a C-methylol group, an aldehyde and mixtures thereof.

6. The polymer of claim 5 wherein said polymer containing an unsaturated carbonyl function is an unsaturated polyester of a polycarboxylic compound and a polyhydric alcohol.

7. The polymer of claim 6 wherein the nucleophilic compound is ammonia.

8. The polymer of claim 6 wherein the nucleophilic compound is aniline.

9. The polymer of claim 6 wherein the aldehyde reacted with said nucleophilic group is formaldehyde.

10. A composition comprising the polymer of claim 6 when cured.

11. The polymer of claim 7 wherein the compound having a C-methylol group is a resole.

References Cited UNITED STATES, PATENTS 3,398,103 8/1968 *Kuhlkamp et a1. 260-850 3,407,152 IO/1968 Kuhl-kamp et a1. 260-850 3,363,025 1/1968 Fitko et a1. 260841 OTHER REFERENCES Nikitina et al., Nucleophilic Additions to Unsaturated Polyesters, Polymer Science, U.S.S.R., vol. 6, 1964, pp. 2374-2377.

JOHN C. BLEUTGE, Primary Examiner US. Cl. X.R.

1l7128.4, 132 BF, 155 L, 161 L; 156--331, 332, 335; 260-48, 50, 51.5, 55, 59', 67 UA, 828, 841, 842, 843, 849, 850, T 

